Control of pests with o,s-dialkyl-s-(4-oxa-1,2,3-benzatriazinyl)-dithiaphosphates

ABSTRACT

Benztriazinonylmethyl organophosphorus esters of the formula   WHEREIN R1 represents alkoxyalkyl with 1 to 5 and 1 to 3 carbon atoms respectively in each of the moieties or alkylthioalkyl with 1 to 5 and 1 to 3 carbon atoms respectively in each of the moieties, and R2 represents alkyl with 1 to 5 carbon atoms, processes for their manufacture and their use in pest control.

United States Patent Drabek July 1, 1975 [5 CONTROL OF PESTS WITH3,622,578 11/1971 Rigterink 260/248 4 1 2 3 3,682,910 8/1972 Colln260/248 TRIAZINYL)-DITHIAPHOSPHATES Primary ExaminerAlbert T. Meyers[75] Inventor: Jozef Drabek, Allschwil, Switzerland Assistant ExaminerD' Robinson Attorney, Agent, or F irmFrederick H. Rabin [73] Ass1gnee:Ciba-Geigy Corporation, Ardsley,

[57] ABSTRACT [22] Flled: 1974 Benztriazinonylmethyl organophosphorusesters of the [21] Appl. No.: 495,459 formula Related US. ApplicationData 0 O 11 [6 Division of Ser. No. 315,971, Dec. 18, 1972, Pat. R S |1c No. 3,845,053. PS CH N R 0 [30] Foreign Application Priority Data NDec. 23, 1971 Switzerland 18828/71 \\N Nov. 7. 1972 Switzerland 16185/72C(il. wherein R1 represents alkoxyalkyl with l to 5 and 1 to 5 8 d424/200 3 carbon atoms respectively in each of the moieties or 1e 0 earcalkylthioalkyl with l to 5 and 1 to 3 carbon atoms spectively in each ofthe moieties, and R represents [56] References Clted alkyl with 1 to 5carbon atoms, processes for their UNITED STATES PATENTS manufacture andtheir use in pest control. 3,131,186 4/1964 Magee et a1. 260/24953,309,371 3/1967 Curry et a1 260/925 6 Clams, N0 Drawmgs 1 2 CONTROL OFPESTS WITH sodium or potassium, ammonium or alkylammonium O,S-DIALKYL-S-(4-OXA-1,2,3-BENZA- with 1 to 5 carbon atoms.

TRIAZINYL)-DITHIAPHOSPHATES Suitable acid binding agents are: tertiaryamines, e.g.

trialkylamines, pyridines, pyridine bases, dialkyl ani- This is adivision of application Ser. No. 315,971, 5 lines; inorgan bases, Suchas hydridesi y d s; filed on Dec, 18, 1972, w US, P N 3,845,053,carbonates and bicarbonates of alkali and alkaline The re nt in tirelates Qt b ln-i i learth metals. During the reactions it is sometimesnecmethyl organophosphorus esters, processes for their essary to use acatalyst, -g PP or pp Chloridemanufacture and their use in pest control.Processes and can be Ca d O t at normal The benztriazinonylmethylorganophosphorus esters Pressure, at a temperature from to and in havethe formula solvents or diluents.

Examples of suitable solvents or diluents are: ether and etherealcompounds, such as diethyl ether, dipro- O pyl ether, dioxan,tetrahydrofuran; amides, such as 0 ll N,N-dialkylated carboxylic amides;aliphatic, aromatic, ll C and halogenated hydrocarbons, in particularbenzene, P'S-CH2 N toluene, xylenes, chloroform, chlorobenzene;nitroles, (1) l i such as acetonitrile, dimethyl sulphoxide; alcohols,such as ethanol and ketones, such as acetone, ethyl N methyl ketone, andwater.

The starting materials of the formulae II, III and IV are known and canbe manufactured by methods analogous to those described in theliterature.

The insecticidal action of analogous compounds is disclosed in theliterature, but by comparison the compounds of the formula I havesurprisingly a markedly The alkoxyalkyl, alkylthioalkyl and alkyl groupstronger and more lasting action against all development stages, such aseggs, larvae, nymphs, pupae and Wl'llCh are possible for R or R may bebranched or adults, of insects, such for example, as those of thefamstraight-cham. Examples of such groups include: i

ilies. Acrldidae, Blattidae, Gryllidae, Gryllotalpidae, methyl, ethyl,propyl, lsopropyl, n-, 1-, sec. and tert.bu-

Tett1gmndae, Ctmtctdae, Phyrrhocoridae, Reduvndae, mpentyl methoxymethylethoxymethyl methoxil Aphididae Delphacidae Diaspididae Pseudococthylethoxyethyl methylthiomethyl methylthioethyl, e cidae, Chrysomelidae,Coccmellidae, Bruchldae,

wherein R represents alkoxyalkyl with l to 5 and 1 to 3 carbon atomsrespectively in each of the moieties or alkylthioalkyl with l to 5 and lto 3 carbon atoms re- 25 spectively in each of the moieties, and Rrepresents alkyl with l to 5 carbon atoms.

ethylthlomethyl and ethylthloethyl' Scarabaeidae, Dermestidae,Tenebrionidae, Curcu Preferred compounds on account of then action are 5lionidae Tineidae Noctuidae Lymantriidae Pyrali those of the formula I,wherein R represents methoxydae Ganeriidae bulicidae l p stonioxydaeethyl, ethoxyethyl or ethylthioethyl, and R represents Mugcidaeeaniphoridae tryzpetidae, Pdlicidae. methyl or ethyl- The compounds ofthe formula I also act against eggs,

The compounds of the formula I can be manufac' larvae and adults ofrepresentatives of the order Acatured by the following methods WhlCh areknown in the 40 rina Such as mites Spider mites and ticks egof the art:

o t u Rls IL-SH x C a) R 2 f acid binding 5 2 N agent (II) N (III) 0 0R18 n n P5146 C R2 XCH2N I I N (III) n the fOrmUlfl 11 to 1V, 1 and 2have the meanmgs families lxodidae, Argasidae, 'l'etranychidae and givenfor the formula I, X represents chlorine or bro- D id mine and Merepresents an alkali metal, in Particular By addition of toherinsecticides and/or acaricides it O-methyl-S-methyl-amidothiophosphateTOR) O-methyl-O-(2,5-dichloro-4-bromophenyl)-benz0- thiophosphate(PHOSVEL) 0,0,0,0-teti'apropyldithiophosphate3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-crotonamide0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL)0,0-diethyl-S-(N-isopropylcarbamoylmethyldithiophosphate (PROTHOATE)S-N-( l-cyano-lmethylethyl)carbamoylmethyldiethylthiolphosphate(CYANTHOATE) S-( 2-acetamidoethyl )-0,0dimethyldithiophosphateHexamethylphosphoric acid triamide (HEMPA)0,0-dimethyl-O-(2chloro-4-nitrophenyl)thiophosphate (DICAPTHON)0,0-dimethyl-O-p-cyanophenyl (CYANOX)O-ethyl-O-p-cyanophenylthiophosphate0,0-diethyl-O-2,4-dichlorophenylthiophosphate (DICHLORFENTHION)-dichlorophenyl-O-methylisopropylamidothiophosphate0,0-di-(B-chloroethyl)-O-(0,0-diethyl-O-Z,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL)dimethylp-(methylthio)phenylphosphate0,0-dimethylO-p-sulphamidophenylthiophosphate O-[p-( p-chlorophenyl)azophenyl 0,0-dimethylthiophosphate (AZOTHOATE)O-ethyl-S-4-chlorophenyl-ethyldithiophosphateO-isobutyl-S-p-chlorophenyl-ethyldithiophosphate0,0-dimethyl-S-p-chlorophenylthiophosphate0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate0,0-diethyl-p-chlorophenylmercaptomethyldithiophosphate(CARBOPHENOTHION) 0,0-diethyl-S-p-chlorophenylthiomethylthiophosphate0,0-dimethyl-S(carbethoxy-phenylmethyl)dithiophosphate (PHENTHOATE)0,0-diethyl-S-(carbofluoroethoxy-phenylmethyl)- dithiophosphate0,0-dimethyl-S-carboisopropoxy-phenylmethyl)- dithiophosphate0,0-diethyl-7-hydroxy 3,4-tetramethylenecoumarinyl-thiophosphate(COUMITHOATE) 2-methoxy-4-H-l ,3 ,2-benzodioxaphosphorin-2- sulphide0,0-diethyl-O-(5-phenyl-3 isooxazolyl)thiophosphate2-(diethoxyphosphinylimino)-4-methyl-1,3-

dithiolane tris-(Z-methyl-l-aziridinyl)-phosphine oxide (ME- TEPA) S-(Z-chloro- 1 -phthalimidoethyl )-0,0-diethyldithiophosphateN-hydroxynaphthalimido-diethylphosphatedimethyl-3,5,6-trichloro-2-pyridylphosphate 0,0-dimethyl-O-( 3,5,6-trichloro-2-pyridyl )thiophosphate S-2-(ethylsulphonyl)ethyldimethylthiolphosphate (DlOXYDEMETON-S-METHYL)diethyl-S-2(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON)bis-0,0-diethylthiophosphoric acid anhydride (SUL- FOTEP) dimethvll,3di( carbomethoxy l -propen-2-yl- (MONI- thiophosphate 7 6 phosphatedimethyl-(2,2,2-trichloro-1-butyr0xyethyl)phosphate (BUTONATE)0,0-dimethyl-O-(2,2-dichloro-l-methoxyvinyl)phosphatebis-(dimethylamido)fluorophosphate (DIMEFOX)3,4-dichlorobenzyl-triphenylphosphoniumchloridedimethyl-N-methoxymethylcarbamoylmethyldithiophosphate (FORMOCARBAM)0,0-diethyl-O(2,2-dichloro-lchloroethoxyvinyl)- phosphate0,0-dimethyl-O-( 2,2-dichlorol -chloroethoxyvinyl)phosphateO-ethyl-S,S-diphenyldithiolphosphateO-ethyl-S-benzyl-phenyldithiophosphonate0,0-diethyl-S-benzyl-thiolphosphate0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphateMETHYLCARBOPHENOTHION) 0,0-dimethyl-S-(ethylthiomethyl)dithiophosphatediisopropylaminofluorophosphate (MIPAFOX)0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTHION)bismethylamido-phenylphosphate 0,0-dimethyl-S-(benzenesulphonyl)dithiophosphate 0,0-dimethyl andO)-ethylsulphinylethylthiophosphate 0,0-diethyl-O-4-nitrophenylphosphatetriethoxy-isopropoxy-bis(thiophosphinyl)disulphide 2-methoxy-4H-l ,3,Z-benzodioxaphosphorin-2-0xide octamethylpyrophosphoramide (SCHRADAN)bis-(dimethoxythiophosphinylsulphido)- phenylmethaneN,N,N,N-tetramethyldiamidofluorophosphate (DIMEFOX)O-phenyl-O-p-nitrophenyl-methanethiophosphonate (COLEP)O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N- methylamidothiophosphate(NARLENE) O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphonate0,0-diethyl-O-(4-methylmercapto-3,5-

dimethylphenyl )-thiophosphate4,4-bis-(0,0-dimethylthiophosphoryloxy)-diphenyl disulphide 0,0-di-(62-chloroethyl)-O-(3-chloro-4-methylcoumarinyl-7 )-phospha'te S-(l-phtha1imidoethyl)-0,0-diethyldithiophosphate 0,0-dimethyl-O-(3-chloro4- diethylsulphamylphenyl)-thiophosphateO-methyl-O-(Z-carbisopropoxyphenyl)-amidothiophosphate5-(0,0-dimethylphosphoryl-6-chloro-bicyclo(3.2.0)-heptadiene (1,5)O-methyl-O-(Z-i-propoxycarbonyl-1-methy|vinyl)- ethylamidothiophosphate.

Nitrophenols and Derivatives 4,6-dinitro--methylphenol, sodium salt[Dinitrocresol] dinitrobutylphenol-(Z ,2 ,2 )-triethanolamine salt2-cyclohexyl-4,6-dinitrophenyl [Dinex] 2-(l-methylheptyl)-4,-dinitrophenyl-crotonate [Dinocap]Z-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton]Miscellaneous aldoxime) O-Z-diphenyl-N-methylcarbamate2-(N-methylcarbamyl-oximino)-3-chlorobicyclo[2.2. l ]heptane 2-(N-methylcarbamyl-oximino bicyclo[2.2. 1 ]heptane3-isopropylphenyl-N-methyl-N-chloroacetalcarbamate3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamate o2,2-dimethyl-4-chloro 2,3-dihydro-7- benzofuranyl )-N-methyl-carbamateO-( 2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl-N- methylcarbamateO-naphthyl-N-methyl-N-acetahcarbamate -5 ,6,7,8-tetrahydronaphthyl-N-methyl-carbamate3-isopropyl-4-methylthio-phenyl-N- methylcarbamate 3,S-dimethyl-4-methoxy-phenyl-N-methylcarbamate3-methoxymethoxy-phenyl-N-methylcarbamate3-alloyloxyphenyl-N-methylcarbamate2-propargylosymethoxy-phenyl-N-methyl-carbamate2-allyloxyphenyl-N-methyl-carbamate4-methoxycarbonylamino-3-isopropylphenyl-N- methyl-carbamate 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamateZ-y-methylthiopropylphenyl-N-methyl-carbamate 3-(oz-methoxymethyl2-propenyl )-phenyl-N-methylcarbamate2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate 4-(methyl-propargylamino-3 ,5-xylyl-N-methylcarbamate 4-(methyl-'y-chloroallylamino)-3,5-xylyl-N-methylcarbamate 4-(methyl-B-chloroallylamino )-3 ,5-xylyl-N-methylcarbamate l-(B-ethoxycarbonylethyl )-3-methyl-5-pyrazolyl- N,N-dimethylcarbamate3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)phenyl-N-methylcarbamatel,3-bis(carbamoylthio)-2-(N,N-dimethylamino)- propanehydrochloride5,S-dimethylhydroresorcinoldimethylcarbamate2-[ethyl-propargylamino]-phenyl-N- methylcarbamateZ-[methyl-propargylamino -phenyl-N- methylcarbamate4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylamino1-3,5-xylyl-N-methylcarbamate 2[allyl-isopropylaminophenyl-N-methylcarbamate3-[allyl-isopropylamino]-phenyl-N-methylcarbamate ChlorinatedHydrocarbons y-hexachlorocyclohexane [GAMMEXANE; LIN- DAN; y HCH]l,2,4,5 ,6,7,8,8-octachlor0-3a,4,7,7a'tetrahydro-4,7-

methylene indane [CHLORDAN]1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-

methylene indane [HEPTACHLOR] 1,2,3 ,4, l 0, l O-hexachlorol ,4,4a,5,8,Sa-hexahydroendol ,4-exo-5,8-dimethanonaphthalene [AL- DRIN] l,2,3,4, lO, l 0-hexachloro-6,7-epoxyl,4,4a,5,6,7,8,8a-octahydro-exol ,4,endo-5,8- dimethanonaphthalene [DIFLORIN] l,2,3,4, l 0, lO-hexachloro-5,7-epoxyl,4,4oz,5,6,7,8,8a-octyhydro-endo-endo-S,8-

dimethanonaphthalene [ENDRIN] The compounds of the formula I may be usedas pure active substance or together with suitable carriers and- /oradditives. Suitable carriers and additives can be solid or liquid andcorrespond to the substances conventionally used in formulationtechnique such, for example, as solvents, dispersants, wetting agents,adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sparys, tosolutions, or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention may also be made ofcattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take, and be used in, the following forms.

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,S10 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formalde hyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predeterminable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/literto 600 g/liter can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting 1e carrier with theactive substance and carriers and lbsequently comminuting the product.

To these mixtures can also be added additives which abilise the activesubstance and/or non-ionic, anionic Id cationic surface activesubstances, which, for exnple, improve the adhesion of the activeingredients 1 plants or parts of plants (adhesives and agglutimts)and/or ensure a better wettability (wetting gents) and dispersibility(dispersing agents). Exam es of suitable adhesives are the following:olein/chalk ixture, cellulose derivatives (methyl cellulose, car-)xymethyl cellulose), hydroxyethyl glycol ethers of onoalkyl and dialkylphenols having 5 to ethylene :ide radicals per molecule and 8 to 9carbon atoms in e alkyl radical, lignin sulphonic acids, their alkalieta] and alkaline earth metal salts, polyethylene glyl ethers(carbowaxes), fatty alcohol polyethylene col ethers having 5 to ethyleneoxide radicals per Jlecule and 8 to 18 carbon atoms in the fatty alcohol)iety, condensation products of ethylene oxide/prolene oxide, polyvinylpyrrolidones, polyvinyl alcols, condensation products of urea andformaldehyde, d also latex products.

The water-dispersible concentrates of the active submce, i.e. wettablepowders, pastes and emulsifiable ncentrates, are agents which can bediluted with tter to any concentration desired. They consist of acesubstance, carrier, optionally additives which staise the activesubstance, surface-active substance d anti-foam agents and, optionally,solvents. Wettable powders and pastes are obtained by mixing d grindingthe active substances with dispering ants and pulverulent carriers insuitable apparatus til homogeneity is attained. Suitable carriers are,for ample, those mentioned for the solid forms of appli- :ion. In somecases it is advantageous to use mixtures different carriers. Asdispersing agents there can be :d, for example, condensation products ofsulphozed naphthalene and sulphonated naphthalene derivves withformaldehyde, condensation products of ahthalene or naphthalenesulphonic acids with pheand formaldehyde, as well as alkali, ammoniumand aline earth metal salts of lignin sulphonic acid, in adion,alkylaryl sulphonates, alkali and alkaline earth tal salts of dibutylnaphthalene sulphonic acid, fatty ohol sulphates such as salts ofsulphated hex- :canols, heptadecanols, octadecanols, and salts of phatedfatty alcohol glycol ethers, the sodium salt of oyl ethionate, thesodium salts of oleoyl methyl tauditertiary glycols dialkyl dilaurylammonium chloand fatty acid alkali and alkaline earth metal salts.uitable anti-foam agents are silicones. 'he active substances are mixed,ground, sieved and lined with the additives cited hereinabove in such anner that, the size of the solid particles does not exd 0.02 to 0.04 tin wettable powders, and 0.03 p. in tes. To produce emulsifiableconcentrates and tes, dispersing agents such as those cited above, oricsolvents, and water are used. Examples of suit- 2 solvents are:alcohols, benzene, xylene, toluene, ethyl sulphoxide, and mineral oilfractions which between 120 and 350C. The solvents must be :ticallyodourless, not phytotoxic, and inert to the ve substances. urthermore,the agents according to the invention be applied in the form ofsolutions. For this pure the active substances, or several activesubstances he general formula I, are dissolved in suitable oricsolvents, mixtures of solvents or in water. Aliphatic and aromatichydrocarbons, chlorinated deriva tives thereof, alkyl naphthalenes, andmineral oils, singly or in admixture with each other, can be used asorganic solvents.

The content of active substance in the above described agents is between0.1 to 95%, in which connection it should be mentioned that, in the caseof application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 10 99.5% oreven pure active substance.

The active substances of the formula I can, for example, be formulatedas follows:

Dusts The following substances are used to manufacture (a) a 5% and (b)a 2% dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of activesubstance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances aremixed with the carriers and ground. Granulesgranules: Y

and dissolved with 6 parts of acetone; the polyethylene glycol and cetylpolyglycol ether are then added. The thus obtained solution is sprayedon kaolin, and the acetone subsequently evaporated in vacuo.

Wettable powder tion of (a) a 40%, (b) and (c) a 25% wettable powder;

The following constituents are used for th e preparaand (d)'a 10% 40parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicicacid.

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), I

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr, I

46 parts of kaolin.

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitdium sulphate. Thebenzene is distilled off to give the compound of the formula o H 0,11001-: CH s u c a 2 2 rsca u with a refraction of n,, "=1.58 l 2.

The following compounds are also manufactured in analogous manner:

0 0 ll C2H5SC.-I2C;{2S\H c f PSCH2 N 11 1, 0091 11 o 0 1| cu oca ca soi0 P-SCH2N n 23 1,59

0 H o l 2 J Ll 0 ll (2 H OCH CH s c 2 5 2 2 PS-CH2N CH O ll I 0 N b.EXAMPLE 2 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorohydrin,

94 parts of benzine (boiling limits l60-l90C).

EXAMPLE 1 O-ethyl-S-ethoxyethyl-S-[4-oxo-1,2,3-benzotriazin- 3 4H)-yl-methyl]-phosphorodithioate l [.3 g of N-chloromethylbenzazimide and17 g of the potassium salt of O-ethyl-S-ethoxyethyldithiophosphoric acidare suspended in 100 ml of acetone at room temperature. The mixture isstirred for 1 hour at room temperature and for 5 hours at 55C. Thereaction mixture is cooled and stirred with 300 ml of ice water. Theprecipitated oil is taken up in 100 ml of benzene, the benzene layerisolated, washed with 3% Na CO solution and with water, and subsequentlydried with so- Insecticidal Ingest Poison Action Cotton plants weresprayed with a 0.05% aqueous active substance emulsion (obtained from a10% emulsifiable concentrate).

After the spray coating had dried, the cotton plants were populated withSpodoptera littoralis or Heliothios virescens larvae (L The test wascarried out at 24C and 60% relative humidity.

in the above test, the compounds according to Example l displayed goodinsecticidal ingest poison action against Spodoptera and Heliothislarvae.

EXAMPLE 3 Action Against Chilo Suppressalis Six rice plants at a time ofthe variety Caloro were transplanted in plastic pots (diameter at thetop=l7 cm) and reared to a height of about 60 cm. Infestation with Chilosuppressalis larvae (L,; 3-4 mm in length) took place 2 days after theactive substance has been applied in granule form to the paddy water(rate of application: 8 kg of active substance per hectare).

Evaluation of the insecticidal action ensued 10 days afterapplication ofthe granules.

In theabove test, the compounds according to Example I acted againstChilo suppressalis.

Five adult ticks or 50 tick larvae were counted into test tube andimmersed for l to 2 minutes in 2 ml of n aqueous emulsion series eachcontaining 100, 10, 1 nd 0.1 ppm of test substance. The tube was then:aled with the standardised cotton wool plug and :00d on its head so asto enable the cotton wool to ab- )rb the active substance emulsion.

In the case of the adults evaluation took place after weeks, and in thatof the larvae after 2 days. Each test 'as repeated twice.

B. Boophilus microplus (larvae) Tests were carried out with sensitiveand 20 OP :sistant larvae with a dilution series analogous to that sedin test A. (The resistance refers to the tolerability f diazinon).

In these tests, the compounds according to Example acted against adultsand larvae of Rhipicephalus ursa and sensitive and OP-resistant larvaeof Boophi- [S microplus.

EXAMPLE 5 Acaricidal action Phaseolus vulgaris (plants) were overlaidwith an in- :sted piece of leaf from a mass culture of Tetranychusrticae 12 hours before the test for acaricidal action. he mobile stageswhich had spread ovet the plants ere sprayed with the emulsified testpreparation from chromatography atomiser so that the spray broth did atrun off. The number of living and dead larvae, iults and eggs wereevaluated after 2 to 7 days under stereoscopic microscope and the resultwas expressed percentages. During the interim, the treated plants erekept in greenhouse compartments at C.

In the above test, the compounds according to Exame I acted againstadults, larvae and eggs of Tetranyius urticae.

EXAMPLE 6 Action Against Soil Nematodes To test the action against soilnematodes, the active .bstances were applied to, and intimately mixedwith, Iil infected with root gall nematodes (Meloidgyne areiria), in thespecifically indicated concentrationsflmediately afterwards, tomatocuttings were planted in e thus prepared soil in a series of tests, andafter a aiting time of 8 days tomato seeds were sown in anher testseries.

In order ot assess the nematocidal action, the galls 'esent on the rootswere counted 28 days after plantg and sowing respectively.

in this test, the active substances according to Exame I display goodaction against Meloidgyne arenaria. I claim:

1. A pesticidal composition for combatting pests sected from the groupconsisting of insects, acarids, and :matodes comprising (1) as activeingredient a pestidally effective amount of a compound of the formulawherein R represents alkoxyalkyl with 1 to 5 and l to 3 carbon atomsrespectively in each of the moieties, or alkylthioalkyl with'lto 5 and 1to'3 carbon atoms respectively in each of "the moieties and R representsalkyl with l to 5 carbon atoms, and (2) a suitable carrier.

2. A method for combatting pests selected from the group consisting ofinsects, acarids and nematodes, which comprises applying thereto apesticidally efffective amount of acompound of the formula RS 0 .c 1 uSCH2-N I R0 5. A method according to claim 3 in which the compound is 6.A method according to claim 3 in which the compound is 2 ,l c n o ll) s

1. A PESTICIDAL COMPOSITION FOR COMBATTING PESTS SELECTED FROM THE GROUPCONSISTING OF INSECTS, ACARIDS, AND NEMATODES COMPRISING (1) AS ACTIVEINGREDIENT A PESTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA2. A method for combatting pests selected from the group consisting ofinsects, acarids and nematodes, which comprises applying thereto apesticidally efffective amount of a compound of the formula
 3. A methodaccording to claim 2 in which R1 represents methoxyethyl, ethoxyethyl orethylthioethyl, and R2 represents methyl or ethyl.
 4. A method accordingto claim 3 in which the compound is
 5. A method according to claim 3 inwhich the compound is
 6. A method according to claim 3 in which thecompound is